Benzanrido-azo-2-hydroxy-3-(carboxanilido-azo-phenyl)-naphthalene compounds

ABSTRACT

WHEREIN R REPRESENTS AN ALKYL, PHENYL OR NAPHTHYL RRADICAL, X HALOGEN, METHYL OR PHENOXY AND AR A PHENYLENE OR NAPHTHYLENE RADICAL ARE VALUABLE PIGMENTS FOR COLORING PLASTICS IN RED SHADES.   AR-NH-CO-)NAPHTHALENE   1-((2-X,4-Y,5-(R-NH-CO-)PHENYL)-N=N-),2-HO,3-(C6H5-N=N-   DISAZO COMPOUNDS OF THE FORMULA

United States Patent 3,726,853 BENZANRIDO-AZO Z HYDROXY-3-(CARBOX-ANILIDO-AZO-PHENYL)-NAPHTHALENE COM- POUNDS Emil Stocker, Riehen, GeorgAnton Klein, Bottmingen,

Basel-Laud, and Ernfred Schnabel, Reinach, Basel- ]Land, Switzerland,assignors t0 Ciha-Geigy AG, Basel, Switzerland No Drawing. Filed July14, 1970, Ser. No. 54,857 Claims priority, application Switzerland, July16, 1969, 10,831/69 Int. Cl. C09b 31/06 US. Cl. 260-188 11 ClaimsABSTRACT OF THE DISCLOSURE Disazo compounds of the formula wherein Rrepresents an alkyl, phenyl or naphthyl radical, X halogen, methyl 'orphenoxy and Ar a phenylene or naphthylene radical are valuable pigmentsfor coloring plastics in red shades.

DESCRIPTION OF THE INVENTION The present invention relates to new disazocompounds, to their use for the pigmenting of high-molecular organicmaterial, and to the compositions thereof.

It has been found that compounds of Formula I (I) wherein R representsan aryl group or an alkyl group,

X represents chlorine, bromine, the methyl group, the phenoxy group, orthe phenoxy group substituted by 1 to 3 chlorine atoms, or by 1 to 2methyl groups,

Y represents hydrogen, or also chlorine if X is. chlorine,

and

Ar represents an arylene group, and the benzene nucleus A can also benon-ionically substituted,

are valuable pigments.

Especially valuable are pigments of Formula I wherein R represents aphenyl radical optionally substituted by 1 to 3 chlorine atoms or themethyl group Ar represents the 1,4-phenylene group optionallysubstituted by a chlorine atom, and A is optionally substituted by achlorine atom.

Compared to known pigments of similar structure, the new disazo pigmentsare distinguished by their purity andintensity, by better fastness tomigration in polyvinyl chloride, as well as by a good fastness to light,to crosslacquering, to weather and to heat.

For example, in Formula I, Ar represents an unsubstituted or anon-ionically substituted 1,4-phenylene group or 1,4-naphthylene group.If the benzene nucleus A is substituted, then suitable substituents arein particular, chlorine alkyl groups having 1 to 4 carbon atoms oralkoxy groups having 1 to 4 carbon atoms such as the methyl 3,726,853Patented Apr. 10, 1973 group or the methoxy or ethoxy group, alsotrifiuoromethyl groups or nitro groups. If R denotes an alkyl group,then this is preferably a lower alkyl group having e.g. 14 carbon atoms,especially the methyl group. Suitable aryl groups are phenyl ornaphthyl, which can be substituted, such as, e.g. by halogen, methyl,met-boxy, trifluoromethyl, methoxycarbonyl, or acylamino groups.

The pigments of Formula I according to the invention can be produced bycoupling the diazonium compound of an amine of Formula II wherein Z=H orCH --W, whereby W stands for the radical of a primary or secondaryamine; or by coupling the diazonium compound of an amine of Formula IV IIH2 with a compound of Formula III, and subsequently condensing it witha compound of Formula V RNH or by condensing a compound of Formula VINHgAr-N=N@ with a compound obtained by the coupling of a diazoniumcompound of an amine of Formula II with a coupling component of FormulaVII COOH (VII) In the case of the compounds of Formulae III and VII, inso far as Z represents the -CH -W-group, these are so-called Man-nichbases (op, e.g. the German patent specification 1,257,312).

The coupling is advantageously performed in an aque ous, preferably acidsolution, and at elevated temperature, optionally in the presence of aninert solvent or dispersing agent. Suitable solvents are water-misciblesolvents such as lower alcohols, e.g. methanol, ethanol, ethylene glycolmonomethyl ether or ethylene glycol .monoethyl ether, lower ketones,e.g. acetone, and tertiary nitrogen bases, e.g. pyridine, and alsodimethylformamide, also certain non-water-miscible solvents such as,optionally, halogenated or nitrated hydrocarbons, e.g. toluene,chlorobenzene and nitrobenzene. Suitable dispersing agents are, e.g.addition products of alkylene oxide, especially ethylene oxide, withfatty alcohols or fatty acids, or condensation products of naphthalenesulphonic acids with formaldehyde.

The pigment produced according to the invention is isolated, washed,dried and pulverised. It can be used direct for pigmenting; butpreferably it is firstly purified by means of an aftertreatment in anorganic solvent at elevated temperature.

Preferred pigments are those of Formula I wherein Ar represents the1,4-phenylene group or the 1,4-naphthylene group, and R denotes abenzene radical or naphthylene radical optionally non-ionicallysubstituted, particularly a benzene radical substituted by 1 to 3chlorine atoms and/ or 1 to 2 methyl groups, by trifiuoromethyl groupsand/ or methoxy groups and/or by a methoxycarbonyl group and/or anacylamino group. Of these, such compounds are especially preferredwherein X stands for chlorine, particularly compounds with R denoting aphenyl group substituted by l to 3 chlorine atoms, preferably in the2,4, S-position, and Y denoting hydrogen.

The disazo compounds according to the invention are suitable for thepigmenting of high-molecular organic 4 coupling is completed, the formedred pigment is filtered off, washed with water, and dried at 70.

After being ground, the pigment is used direct for the pigmenting ofhigh-molecular organic material; or it is further purified by means of asubsequent heat treatment in an organic solvent, e.g. by being heatedfor minutes, with stirring, in 150 ml. of o-dichlorobenzene to 132-135being then allowed to cool to 50, filtered off, washed with methanol,and dried. In lacquers it exhibits a red shade, has fastness tocross-lacquering and to heat, and has very good fastness to light. Insoft polyvinyl chloride it is likewise distinguished by purity of shadeand strength of colour, and by a very food fastness to migration andheat, and by excellent fastness to light.

EXAMPLE 2 materials, e.g. in printing inks for the printing trade,

in lacquers having an oily base, such as in linseed-oil paints, orhaving an aqueous base, such as in dispersion paints, in lacquers ofvarious types such as, e.g. in nitro lacquers or in stoving-enamels,particularly, however, for the pigmenting of synthetic materials such aspolyolefins, cg. polypropylene, and preferably polyvinyl chloride, alsofor the pigmenting of synthetic fibres such as polyester,polyaciylonitrile and polyolefin fibres. They impart to these materialsbeautiful and full red dyeings in various shades orwith the simultaneousaddition of white pigments such as titanium oxide corresponding pasteldyeings. The dyeings have good fastness to migration, heat, weather andlight; the lacquers are distinguished by a good fastness tocross-lacquering.

The temperatures are given in degrees Centigrade in the followingexamples.

EXAMPLE 1 Q I 1 C1 Into 40 ml. of sulphuric acid/nitrosyl sulphuric acidmixture containing 2.55 g. of HO SO-NO are added, with stirring, 6.31 g.of ground 4-chloro-3-aminobenzoic acid-2',4-dichloroanilide. After 30minutes, the obtained solution is poured, in a thin stream, into astirred mixture of 100 ml. of ice water and 100 g. of crushed ice;

methanol and 26.6 g. of 30% sodium hydroxide solution,

whereby the temperature rises to about 40. The red pigment-suspension issubsequently heated in 30 minutes to 82; this temperature is maintainedfor a further 30 minutes, and the pigment then filtered off hot; it iswashed with water until neutral, and dried at 70.

An amount of 10.0 g. of ground crude pigment is added, with stirring, to150 ml. of o-dichlorobenzene; it is 3.50 g. ,400 mole) of4-chloro-3-arninobenzoic acid-2'-, then heated during 2 hours to140-142", filtered off at 4,5'-trichloroanilide are dissolved, withstirring, in 400 ml. of glacial acetic acid at 45, whereupon 12.0 ml. of10 N hydrochloric acid are also added. A solution of 0.76 g. of sodiumnitrite and 0.5 g. of alkylpolyglycol ether in 100, washed withmethanol, and dried at A yellowish red pigment is obtained which isused, e.g. for the pigmenting of polyvinyl chloride, and which enablesbrilliant scarlet shades having excellent fastness to migration,

200 ml. of water is then plunged into the acetic acid solu- 70 to heatand to light, to be produced.

tion, the mixture immediately heated to 55, and 60 ml. of 2 N sodiumacetate solution are then added. A solution, produced at 20, of 3.80 g.of 2',3-hydroxynaphthoyl-4- aminoazobenzene in 100 ml. of methanol, and50 ml. of 2 N sodium hydroxide solution is thereupon added in 4 minutesat 50-55 to the diazonium compound. When the By proceeding as in Example.1 but using, instead of the 4-chloro-3-aminobenzoicacid-2',4,5-trichloroanilide used there, equimolecular amounts of theamines listed in the following table, pigments are obtained havingproperties similar to those of the pigment of Example 1 or 2,

with the shades given in the 3rd column of the table.

TABLE-Continued Ex. Amine Shade 01 Cl-QNH-C o- I F3C NHg Red.

Red.

Red.

Bluishred.

Red.

The amine of Example 21 can be produced, e.g. as

follows:

3-nitro-4-chlorobenzoic acid is reacted with p-chlorophenol; the acidchloride is produced, and this is con- 35 densed with2,4,5-trichloroaniline, whereupon, in the formed compound, the nitrogroup is reduced to the amino group.

With the same procedure as given in Example 1, but

using equivalent amounts of the following diazo and 40 couplingcomponents, pigments are obtained having similar properties and with theshades shown in the last column.

EXAMPLE 28 To a base mixture consisting of 63 parts by wt. ofemulsion-polyvinyl chloride (K-40), 32 parts by wt. of dioctylphthalate,

3 parts by wt. of epoxy softener (e.g. Advaplast 39), 1.5 parts by wt,of barium-cadmium complex as stabiliser (e.g. Advastab BC 26) and I 0.5part by wt. of a chelator (e.-g. Advastab CH 300) are added 0.5 part byweight of pigment according to Example l, and 5 parts of titaniumdioxide (Rutil), and the Whole is then intimately mixed. The'mixture isrolled,

Ex. Diazo component Coupling component Shade 23 Yellowish Cl NHCO C1 OHred.

I I 01 NH, o ONH- N=N I I O1 Cl 24 C1 Do.

0 H 01- NH-CO-Q-Ol I 1 C ONH N=N C] N I I 25 Red.

C l NH- C 0- C1 0 H I ('31 NH, 0 ONHN=N I I C C 26 C1 Red.

I l C ONH N=N 01 I I CH3 CH3 27 Cl Brown- OH red. 01- NHoo--c1 l C ONH-N=N- 31 NH: g 2

to obtain better pigment dispersion, for 8 hours on mixing rolls withfriction rollers, heated to 160 (one roller rotating at 20 r.p.m., theother at 25 r.p.m.); and thereupon the obtained 0.3 mm. sheet, having apure red shade, drawn oif. The dyeing has very good fastness to lightand to migration, as well as resistance to heat.

EXAMPLE 29 4 parts by weight of the pigment according to Example 2 areground in a ball mill for 24 hours with 96 parts by weight of a mixtureof 50 parts by weight of a 60% solution of coconut-oil fatty acidmodified alkyd-melamine resin having a 32% fatty acid content, inxylene,

30 parts by weight of a 50% melamine resin solution in butanol,

10 parts by weight of xylene, and

10 parts by weight of ethylene glycol monomethyl ether.

The thereby obtained dispersion is sprayed on to sheet metal; this isthen allowed to rest in air for 30 minutes, whereupon the lacquer isstoved for 30 minutes at 120". A brilliant scarlet red film is obtainedhaving very good fastness to light and to weather.

What we claim is:

1. An asymmetrical disazo compound of the formula wherein R representsphenyl or phenyl substituted by chlorine, methyl, methoxy,trifluoromethyl, methoxycarbonyl or acetylamino, or R represents alkylhaving 1 to 4 carbon atoms,

X represents chlorine, methyl, phenoxy, or phenoxy monosubstituted bychlorine,

Y represents hydrogen, or also chlorine if X is chlorine,

and

Ar represents phenylene, naphthylene or phenylene monosubstituted bychlorine or methyl, and the benzene nucleus A is unsubstituted ormonosubstituted by chlorine, or alkyl having 1 to 4 carbon atoms.

2. An asymmetrical disazo compound according to claim 1 wherein Arrepresents 1,4-phenylene or 1,4- naphthylene.

3. An asymmetrical disazo compound according to claim 1 wherein Rrepresents phenyl unsubstituted or substituted by 1 to 3 chlorine atoms,methyl or methoxy, Ar represents 1,4-phenylene or 1,4-phenylenesubstituted by chlorine, X and Y have the meanings given in claim 1, andthe benzene nucleus A is unsubstituted or substituted by a chlorineatom.

4. An asymmetrical disazo compound according to claim 1 wherein Xrepresents chlorine.

5. An asymmetrical disazo compound according to claim 4 wherein Rrepresents benzene substituted by l to 3 chlorine atoms, and Ar denotes1,4-phenylene.

6. An asymmetrical disazo compound according to claim 5 wherein Rrepresents 2,4,5-trichlorophenyl, and Y denotes hydrogen. 7

7. A compound according to claim 1 which is 8. A compound according toclaim 1 which is 9. A compound according to claim 1 which is 10. Acompound according to claim 1 which is 12 11. A compound according toclaim 1 which is 01 CHZOQQHW CI Q 61 l I=N- HHONR WZM References CitedUNITED STATES PATENTS 2,163,074 6/1939 Thoma et a1. 260188 LEWIS GOTTS,Primary Examiner C. F. WARREN, Assistant Examiner US. Cl. X.R.

